Composition for imparting anti-scuff properties to a fibrous article and the resulting article



April 1968 c. A. DUHARTEFRANCIA 3,376,161

COMPOSITION FOR IMPARTING ANTI-SCUFF PROPERTIES TO A FIBROUS ARTICLE AND THE RESULTING ARTICLE Filed NOV. 1, 1965 INVENTOR CAraLos A DuHnRTE- Fnnncm XTTORNEYS 3,376,161 COMPOSITION FOR IMPARTING ANTI-SCUFF PROPERTIES T A FHBROUS ARTICLE AND THE RESULTHNG ARTICLE Carlos A. Duharte-Francia, Evergreen Park, Ill., assignor to Continental Can Company, Inc., New York, N.Y., a corporation of New York Filed Nov. 1, 1963, Ser. No. 320,679 10 Claims. (Cl. 117-461) This invention relates to a composition of matter which may be applied to fibrous masses to impart lubricity and softness thereto; and to the fibrous articles and materials containing such composition. The composition consists of three major components: a first quaternary ammonium chloride having at least two long hydrocarbon groups, a polysiloxane and a second quaternary ammonium chloride containing an alkyl amide group.

Packaging and packing materials for highly finished articles transported in commerce should have a sufficient lubricity and softness so that the surfaces of the articles are not abraded or marred. Materials which meet these general criteria are said to have anti-scuff properties or characteristics and the compositions which are used to modify the usual packaging materials are termed antiscufi coating agents.

In the past anti-scuff coatings have been used with corrugated board and other fibrous materials to soften and to add lubricity thereto so that when articles such as refrigerators, stoves and finished wooden items are rubbed Q against the coating few abrasion and scuff marks result. Such prior art coatings have two major undesirabilities. The protection against abrasion is loW and there is a tendency for the coating material to transfer to the articles being packed. Such coating materials are exemplified by metallic soaps, parafiin, fatty acids, and microcrystalline waxes.

The above difficulties have been overcome by use of the anti-scuff composition of the present invention. The composition may be used as an impregnating substance and a coating for corrugated board, fiberboard, papers and other fibrous articles and materials to attain improved lubricity and softness with very low transfer to articles which come in contact therewith. Such fibrous material when coated with and softened with the novel anti-scuff composition will not mar and abrade the surface of articles which are packaged and shipped in such material.

It is an object of this invention to provide a composition of matter for impregnating fibrous material to impart thereto anti-scuff characteristics comprising in aqueous solution 1 to 10 percent by weight of each of:

(1) A first quaternary ammonium chloride having the type formula of:

(R1)(R2)(R3)(R4).EN C1 quarternary (2) A dimethylpolysiloxane having a molecular weight in the range of 69,000 to 71,000 and,

3) A second quaternary ammonium compound having a type formula of (R6)(R7)(R3) (R NH-CO-CH NCl quarternary The first quaternary ammonium chloride preferably has a structure wherein R and R are methyl groups and R and R are hydrocarbon groups having from 12 to 18 carbon atoms. The second quaternary ammonium chloride R comprises a hydrocarbon group having from 16 to 18 carbon atoms and R is a hydrocarbon group having hydroxyl and alkoxyl groups substituted thereon,

States Patent 0 3,376,161 Patented Apr. 2, 1968 ice while R and R are hydroxy-group substituted hydrocarbon groups.

The preferred composition of matter for carrying out the above objects is present when the R group of the second quaternary ammonium chloride is a substituted ethyl group selected from the class consisting of Z-hydroxy diethoxy ethyl, Z-hydroxy triethoxy ethyl and 2-hydroxy tetraethoxy ethyl and the R and R groups are 2-hydroxy ethyl.

The composition of matter for attaining the above object is preferably constituted of 8 to 10 percent by weight of the first quaternary ammonium chloride, 2 to 5 weight percent of the dimethyl polysiloxane and 1 to 2 percent by weight of the second quaternary ammonium chloride.

It is yet another object of the present invention to provide a composition of matter for impregnating fibrous material to impart anti-scuff characteristics thereto which employs water as a solvent in the amount of approximately percent by weight.

Another object of the present invention is to provide a composition of matter for impregnating fibrous material to impart anti-scuff characteristics thereto by softening and adding lubricity to the fibers thereof comprising in aqueous solution:

(1) A first quaternary ammonium chloride in a concentration of 8 to 10 weight percent having the type formula of:

quarternary where R, and R are methyl groups and R and R are hydrocarbon groups having from 12 to 18 carbon atoms.

(2) A trimethyl siloxy-end-blocked dimethylpolysiloxane of a molecular weight in the range of 69,000 to 71,000 in a concentration of 2 to 5 weight percent, and

(3) A second quaternary ammonium chloride in a concentration of approximately 1-2 percent by weight having the type formula of:

where R is a hydrocarbon group having 16 to 18 carbon atoms in a linear chain, R is a hydroxy and ethoxy containing a hydrocarbon group, and R and R are hydroxycontaining hydrocarbon groups.

The above object is preferably attained when the R group of the second quaternary ammonium chloride is 2- hydroxy triethoxy ethyl, 2-hydroxy diethoxy ethyl or 2- hydroxy tetraethoxy ethyl and the R and R groups of said secondary quaternary ammonium chloride are 2-hydroxy ethyl.

It is yet another object of the present invention to provide a fiber article having at least the outer fibers thereof coated and impregnated with an anti-scuff composition comprising a mixture of a first quaternary ammonium chloride, a dimethyl polysiloxane, and a second quaternary ammonium chloride in the weight ratio ranges of 8 to 10:2 to 5:1 to 2 and the anti-scuff composition being present in a concentration in the range of 0.5 to 1.5 pounds per 1,000 square feet of article surface and being impregnated within the body of the fiber article and in the outer fibers near the surface thereof.

The above object is preferably attained by coating a sized or unsized fiber article by means of roll coaters, curtain coaters, reverse roll coaters, or spray equipment with the composition of matter of the previous objects.

These and other objects will appear from the followin g description and the drawing in which:

The figure shows an enlarged view of a portion of a fibrous article in which the fibers thereof are coated with the novel composition of matter of the present invention.

Referring to the figure showing the fibers greatly enlarged, the fibers 5 which constitute a fibrous article 6 are impregnated and covered over their surfaces with a layer 7 of anti-scuff composition. The fibers 5 may be present in materials such as corrugated board, liner board, paper, cardboard, or other cellulosic fibrous material. It is within the scope of the present invention to impart anti-scufii characteristics to materials of cellulosic origin such as wood fibrous materials, pulp materials, as well as textile fibers.

The coating 7 of the novel anti-scuff composition of the present invention is shown coating the outer surfaces of the individual fibers and the connections between the fibers from the surface 8 into the body 9 of the fibrous article.

When a coating method is employed to contact the fibers with the novel anti-scuff composition, the concentration of the coating on the outermost fibers near surface 8 is expected to be greater than the concentration occurring on the inner fibers at an interior portion 9. As the softness and lubricity of the fibrous article is particularly advantageous at the outermost surface thereof, this result is consistent with the purposes of the present invention.

The anti-scuff composition coated on the fibers 5 of the figure may be most readily described by a description of the coating material in aqueous solution by which it may efiiciently and economically applied to fibrous articles; the water then being driven off in drying. The aqueous solution of the composition of matter for impregnating fibrous articles to impart thereto anti-scuff characteristics has the following components:

This formulation has been used to coat paperboard and then tests for anti-scuff properties carried out in packaging environments. The qualitative results show high protection against article abrasion, low transfer and superior lubricity and softness.

The above specific coating aqueous solution which has been extensively tested may, of course, be varied by varying the parts by weight of the components 1-3. The first quaternary ammonium chloride may be varied between 8 and 10 weight percent while the polysiloxane may be varied between 2 and 5 weight percent and the third component varied between 1 and 2 weight percent while retaining the effectiveness of the anti-scuff properties.

In the above formulation the fifth component is due to the presence of various inert materials in the first three components as they are obtained from commercial channels.

The first quaternary ammonium chloride, component 1 above, is of the general formula of wherein R and R are methyl groups and R and R are hydrocarbon groups. The R and R groups are generally even numbered carbon atom chains of from 12 to 18 carbon atoms.

Table 1 sets out the distribution of R and R groups in the first quaternary ammonium chloride.

4 TABLE I Percent quaternary R and R salt by weight C12 Traces C18 (unsat.) 1-2 C18 (sat.) 65-69 The percentage ranges of the quaternary salts having R and R groups as designated .in Table I are average weights which show the percentage presence of the hydrocarbon groups identified as if the same hydrocarbon chain were both the R and R group on an individual molecule. In reality the groups C12-C18 are mixed and are present in the quaternary ammonium salts as substituted groups on the ammonium chloride in a random manner.

While the majority of the R and R groups of the first quaternary ammonium chloride salt are saturated hydrocarbon chains of 16 and 18 carbon atoms, the inclusion of unsaturated hydrocarbon groups is contemplated as is shown and is within the scope of this invention. The hydrocarbon groups need not be linear but may be branched with the limitation that a linear carbon chain of at least 12 carbon atoms is present.

The polysiloxane, component 2, of the above formulation is dimethyl polysiloxane which is end-blocked with trimethylsiloxy groups and has a molecular weight in the range of 69,000 to 71,000.

The third component is a quaternary ammonium chloride salt having a structural formula of:

quaternary usable for component 1 of the above formulation is available from Armour Industrial Chemical Company under the trade designation of Arquade 2HT-75. A satisfactory polysiloxane has been that available from Dow Corning Corporation, Emulsion 37 which has the type formula of:

in which the average value of n is such that the pure polysiloxane has a viscosity of about 10,000 cs. at 25 C. The value of n is considered to be approximately 950.

The third component may be synthesized by reactions well known in the prior art or may be purchased in known commercial channels.

It is obvious that the illustrative practices are not restrictive; and that the invention can be practiced in many ways Within the scope of the appended claimed subject matter and specifically the anti-scuff composition of the present invention may be coated to fibers of existing fibrous articles or may be admixed therewith during the formation process of the fibrous articles to attain a coatin g and impregnating therein.

I claim:

1. A composition of matter for impregnating fibrous material to impart thereto anti-scuff characteristics comprising in aqueous solution one to ten percent by weight of each of:

(1) a first quaternary ammonium chloride having the type formula of quaternary Where R and R are methyl groups and R and R are hydrocarbon groups having from 12 to 18 carbon atoms,

(2) a dimethylpolysiloxane having a molecular Weight in the range of 69,000 to 71,000 and (3) a second quaternary ammonium chloride having a type formula of (R6) (R7) (R8) trnNn-co-onngN-ol quaternary where R is a hydrocarbon group having from 16 to 18 carbon atoms, R is a hydrocarbon group having hydroxyl and alkoxy groups substituted thereon, and R and R are hydroxyl-group substituted hydrocarbon groups.

2. The composition of matter of claim 1 in which said second quaternary ammonium chloride has a R group of a substituted ethyl group selected from 2-hydroxy diethoxy ethyl, Z-hydroxy triethoxy ethyl and Z-hydroxy tetraethoxy ethyl and R and R groups are 2-hydroxy ethyl.

3. The composition of matter of claim 1 in which said first quaternary ammonium chloride is present in a concentration of 8 to 10 percent by weight, and said dimethylpolysiloxane is present in a concentration of 2 to 5 percent by weight, and said second quaternary ammonium chloride is present in a concentration of 1 to 2 percent by Weight.

4. A composition of matter for impregnating fibrous material to impart anti-scuff characteristics thereto comprising in aqueous solution:

(1) a first quaternary ammonium chloride in a concentration of 8 to 10 weight percent having the type formula of:

(R1) 2) 3) (RON- where R and R are methyl groups and R and R are hydrocarbon groups having from 12 to 18 carbon atoms,

(2) a trimethylsiloxy-end-blocked dimethylpolysiloxane of a molecular weight in the range of 69,000 to 71,000 in a concentration of 2 to 5 Weight percent and (3) a second quaternary ammonium chloride in a concentration of approximately 1-2 percent by weight having the type formula of:

quaternary where R is a hydrocarbon group having from 16 to 18 carbon atoms in a linear chain, R is a hydroxy and ethoxy containing hydrocarbon group, and R and R are hydroxy-containing hydrocarbon groups.

5. The composition of matter of claim 4 in which the R group of said second quaternary ammonium chloride is 2-hydroxy triethoxy ethyl and the R7 and R groups of said second quaternary ammonium chloride are 2-hydroxy ethyl.

6. A fiber article having at least the outer fibers thereof coated and impregnated with an anti-scuff composition comprising a mixture of a first quaternary ammonium chloride, a dimethylpolysiloxane, and a second quaternary ammonium chloride, said first quaternary ammonium chloride having two hydrocarbon groups having 12 to 18 carbon atoms and having two methyl groups, said dimethylpolysiloxane having a molecular weight in the range of 69,000 to 71,000, and said second quaternary ammonium chloride having a type formula of (R6) (R7) (R8) (R NH-CO-CH )NCl quaternary where R is a hydrocarbon group having from 16 to 18 carbon atoms, R is a hydroxy and ethoxy containing hydrocarbon group, and R and R are hydroxy-containing hydrocarbon groups.

7. The fiber article of claim 6 in which said anti-scuff composition is present in the fibers in a concentration in the range of 0.5 to 1.5 pounds per 1,000 square feet of article surface.

8. The fiber article of claim 6 in which the weight ratio of said first quaternary ammonium chloride to said dimethylpolysiloxane and to said second quaternary ammonium chloride is in the range of 8 to 10:2 to 5:1 to 2, respectively.

9. A fiber article having at least the outer fibers thereof coated and impregnated with an anti-scuff composition in a concentration in the range of 0.5 to 1.5 pounds per 1,000 square feet of article surface, said composition comprising a mixture of a first quaternary ammonium chloride, a dimethylpolysiloxane, and a second quaternary ammonium chloride in the Weight ratio ranges of 8 to 10:2 to 5:1 to 2, respectively.

10. The fiber article of claim 9 in which said first quaternary ammonium chloride contains two hydrocarbon groups of 12 to 18 carbon atoms and said second quaternary ammonium chloride has a type formula of:

( 6) 1) s) 5 2)NC1 quaternary where R is a hydrocarbon group having from 16 to 18 carbon atoms, R is a hydroxy and ethoxy containing hydrocarbon group, and R and R are hydroxy-containing hydrocarbon groups.

References Cited UNITED STATES PATENTS 2,691,606 10/1954 Ziliox 117-154 X WILLIAM D. MARTIN, Primary Examiner.

MURRAY KATZ, Examiner.

T. G. DAVIS, Assistant Examiner. 

1. A COMPSOITION OF MATTER FOR IMPREGNATING FIBROUS MATERIAL TO IMPART THERETO ANTI-SCUFF CHARACTERISTICS COMPRISING IN AQUEOUS SOLUTION ONE TO TEN PERCENT BY WEIGHT OF EACH OF (1) A FIRST QUATERNARY AMMONIUM CHLORIDE HAVING THE TYPE FORMULA TYPE FORMULA OF
 6. A FIBER ARTICLE HAVING AT LEAST THE OUTER FIBERS THEREOF COATED AND IMPREGNATED WITH AN ANTI-SCUFF COMPOSITION COMPRISING A MIXTURE OF A FIRST QUATERNARY AMMONIUM CHLORIDE, A DIMETHYLPOLYSILOXANE, AND A SECOND QUATERNARY AMMONIUM CHLORIDE, SAID FIRST QUATENARY AMMONIUM CHLORIDE HAVING TWO HYDROCARBON GROUPS HAVING 12 TO 18 CARBON ATOMS AND HAVING TWO METHYL GROUPS,SAID DIMETHYLPOLYSILOXANE HAVING A MOLECULAR WEIGHT IN THE 